Polyimide-polyamides from maleopimaric acid derivatives



United States Patent O U.S. Cl. 260-47 6 Claims ABSTRACT OF THEDISCLOSURE New compositions of matter are prepared by reacting one moleof various diamines withtwo moles of the monoacid chloride ofmaleopimaric acid (MAC) to give bisamides. These bisamides are fused inmole to mole ratios with various diamines to give head-to-head andtail-to-tail linked, new polyimide-polyamide resins. Newamide-amine-hydrochloride salts of maleopimaric acid are also preparedby reaction of MAC with a large excess of various diamines. The fusionof this product yields a new head-to-tail linked polyimide-polyamideresin. A third product is a new polyimide-polyamide resin prepared bythe reaction of 1 mole of diamine with 1 mole of a triester prepared byreacting MAC with 3 moles of methanol.

The end products are useful for casting water-resistant films and forthe preparation of synthetic fibers.

DISCLOSURE OF INVENTION A non-exclusive, irrevocable, royalty freelicense in the invention herein described, throughout the world for allpurposes of the United States Government, with the power to grantsublicenses for such purposes, is hereby granted to the Government ofthe United States of America.

It is an object of this invention to describe our improved process forthe preparation of the monoacid chloride of maleopimaric acid (MAC). l

It is another object of this invention to describe the preparation ofnew compositions of matter prepared by reacting one mole of variousdiamines with two moles of MAC to give bisamides. These bisamides arefused in mole to mole ratios with various diamines to give head-to-headand tail-to-tail linked, new polyimide-polyamide resins. v, 7

It is still another object of this invention to describe the preparationof new random linked polyimide-polyamide resins by the fusion of MACwith various diamines in mole ratios of 1 to 1. V a

It is a further object of this invention to describe the preparation ofnew amide-amine-hydrochloride salts of maleopimaric acid by reaction ofMAC with a large excess of various diamines. The fusion of this productyields reaction of 1 mole of diamine with 1 mole of a triester preparedby reacting MAC with 3 moles of methanol.

Maleopimaric acid is the well known reaction product of maleic anhydrideand any of the four conjugated dienic resin acids, namely levopimaric,neoabietic, palustric and abietic. The first named acid will react atroom temperature; the other acids require heat. Gum rosin can bemaleated directly and all of the conjugated dienic resin acidspresent-which constitute the major portion of the composition of gumrosin-will be converted to maleopimaric acid, the structure of which'isas follows:

O H CH3 HaC 0% O HaC COHO Maleated'gum rosin can also be converted tothe acid *chloride by reaction with thionyl chloride and used in placeof MAC throughout. This provides a much cheaper raw material.

When 2 moles of MAC are reacted with 1 mole of various diamines, newcompositions of matter called hisamides are formed, the structure ofwhich are:

CH8 CH3 or 0 Ha. o O on on, -C -c 7 II H O O O=C CH3 R NE- in which R isthe residual moiety of the diamines set forth below. A series ofbisamides were prepared employing the following diamines:1,2-ethanediamine, 4,4-oxydiam'line, 1,6-hexanediamine.1,3-propanediamine, paraphenylenediamine, meta-phenylenediamine, and4,4- methylenedianiline. These bisamides are either prepared by thepyridine method or by a modified Scholten-Baumann procedure. Some of thebisamides were prepared by both procedures and gave the same product. Inboth processes, the temperature range used is from C. to roomtemperature.

The fusion of these bisamides (1 mole) with 1 mole of various diaminesyields new polyimide-polyamide resins which have a structure in whichthe repeating unit consists essentially of CH3 11 I HaC R s..-

\C HaC and R is selected from the group consisting of:

These have head-to-head, tail-to-tail linkages. The fusions are carriedout in a test tube with a stream of nitrogen introduced under the meltto help remove the water formed in the reaction. A thermometer isinserted in the melt to determine the fusion temperature. Heat issupplied either by an open flame from a Bunsen burner or by a fluidizedsand bath. Temperatures of fusion are in the range of 225 C. to 375 C.with the preferred temperature range being about 290350 C. The time offusion over an open Bunsen flame varies from 2 to 20 minutes with thepreferred range of about 2-8 minutes. On cooling the polymers are hardglassy solids. Softening points range up to 340 C. via a capillary tubein an oil bath. Solvent resistance is high with most of the polymersbeing insoluble in water, conc. hydrochloric acid, 10% aqueous sodiumhydroxide, benzene, isooctane, pentane, acetonitrile, ethyl acetate,dioxane, glacial acetic acid, carbon tetrachloride, ethyl alcohol,methyl alcohol, and so forth. Molecular weights are usually determinedvia titration of anhydride end groups with base in acetone. Molecularweights via this method range from 2,00ll'to 8,500. The resultinglpolyimide-polya mides can be .cast as films from chloroform solution.The films are hard and tough and resistant-to water and other solvents.Also,-

fibers can be cold drawn from the hot melts. These fibers offer apotential basis for the preparation of a new type of synthetic fiber.

. 4 acid yields the new amide-amine-hydrochloride salt of the followingstructure:

HQG O have an ordered orientation and, depending on the diamine selectedfrom the group listed below, has the structure:

a HaC CE N- and R is any one of Again, the fusion is done in a test tubeas described earlier and the nitrogen sweep serves to remove hydrogenchloride gas as well as water of reaction. The fusion temperadiamines(and triamines) results in the formation of The reaction of 1 mole ofMAC with a large excess (e. g. I i

10 moles) of a diamine in a modified Scholten-Baumann rocedure followedby acidification" with hydrochloric a resin in which the repeating unitis:

Again, the fusion is carried out as described above, the nitrogen streambeing useful to remove hydrogen chloride and water of reaction. Fusiontemperatures, as measured by a thermometer in the melt over an openBunsen flame, range from 225 to 375 with the preferred range being290-325 C. The time of fusion over an open Bunsen flame varies from 2 to20 minutes with the preferred range about 3-8 minutes. The resinsresemble those obtained from the bisamides. They are hard, glassysolids. They are insoluble in all the solvents previously tested. Themolecular weights, by the method previously described, vary from 2,000to 18,000. Films can be cast from chloroform solution, which are hardand tough and very resistant to water and other solvents. Fibers can becold-drawn from hot melts offering a new type of synthetic fibermaterial. The various amines reacted with MAC are: 4,4'-oxydianiline,1,6-hexanediamine, 3,3-iminobispropylamine, 1,2 ethanediamine, 1,3propanediamine, para phenylenediamine, meta phenylenediamine, and4,4-methylenedianiline.

The reaction of MAC with an excess of methanol yields a triester of thefollowing structure:

Fusion of this triester with various diamines yields apolyimidepolyamide resin similar in properties to those obtained fromthe bisamides. The fusion time required is longer, being on the order of1-3 hours in a fluidized sand bath at about 280-310 C. The resins can becold drawn from the hot melt to give fibers, forming the basis for a newtype of synthetic fiber.

Example 1 To 30 ml. of thionyl chloride was added 20 g. of maleopimaricacid and stirred until all solids are in solution. Much gas wasliberated during the process. After standing overnight at roomtemperature, the bulk of the excess thionyl chloride was stripped offunder reduced pressure. Stripping was discontinued when the material inthe pot formed a slush. This was filtered on a sintered glass funnel,triturated with dry ether, and washed with dry ether; yield 16.8 g.equiv. wt. 105.4; [u] 44.4- (c. 2.35 in chloroform). The monoacidchloride of maleopimaric acid (MAC) was recrystallized twice from drybenezene and exhibited no change in optical rotation. The recrystallizedproduct exhibited [a] 44.2 (c. 2.24 in chloroform); M.P. with dec.

and evolution of gas; no characteristic absorption from 220-320 mm.; k(Nujol mull) 5.44 1. (m.) (anhydride), 5.63n (s.) (anhydride), 8.17,u.(s.) (anhydride). (Maleopimaric acid exhibits A (Nujol mull) 5.43,u(m.), 5.6311. (s.) and 8.18u (s.)).

Analysis.-Calcd for C H O Cl (percent): C, 68.80; H, 7.46; Cl, 8.46; O,15.28; equiv. wt. 104.7. Found (percent): C, 68.72; H, 7.39; Cl, 8.36;O, 15.14; equiv. wt. 104.9.

A mixture of 200 g. (0.66 mole) of WG gum rosin and 45 g. (0.46 mole) ofmaleic anhydride were mixed and heated together under nitrogen withstirring for one hour at 200 C. At the end of this time, the ultravioletabsorption spectrum showed that all the conjugated dienic resin acidspresent were maleated. A sample of the maleated rosin weighing 138 g.was dissolved in 300 ml. of thionyl chloride with stirring. A vigorousevolution of gas occurred. Twenty-four hours later the solution wasstripped on a steam bath under reduced pressure to a syrup. An excess ofisooctane was then added to the syrup with stirring and allowed to standovernight. In the morning, the mixture was rubbed in a mortar, collectedby filtration, washed with more isooctane and dried under reducedpressure to give the monoacid chloride of maleated gum rosin as a brownpowder; equivalent weight; found, 119; theory, 105. This maleated acidchloride can be substituted for MAC in all of the following exampleswherever MAC is used.

Example 3 To a solution of 0.034 ml. (0.005 mole) of 1,2-

ethanediamine in 10 ml. of dioxane plus 18 ml. of 10% sodium hydroxidein water was added dropwise a solution of 4.9 g. (0.01 mole) of MAC in40 ml. of dioxane. Magnetic stirring was maintained plus water bathcooling. After one hour, an excess of 3 N hydrochloric acid was added.An oil formed. The supernatant was decanted and fresh water added. Theoil solidified. It was triturated with 1 N hydrochloric acid and waterwashed thoroughly; yield 2.50 g.; neut. equiv. for the bisamide ofmaleopimaric acid, 205; theory 206. The structure of this compound is asfollows:

A solution of 2.0 g. (0.01 mole) of 4,4'-oxybisaniline (0.01 mole) in 10ml. of pyridine was added dropwise to a solution of 8.4 g. (0.02 mole)of MAC in pyridine at -l0 C. with stirring. After 1 hour at roomtemperature an excess of 3 N hydrochloric acid was added plus water. Thesolid was collected and dried, weight 9.2 g.

The equivalent weight was 283; theory 281.

Example 5 A solution of 0.58 g. (0.005 mole), 1,6-hexanediamine in 5 ml.of pyridine was added dropwise to 4.19 g. (0.01 mole) of MAC in ml. ofpyridine with magnetic stirring and water bath cooling. After 1 hour insolution was filtered and an excess of 3 N hydrochloric acid was added.The white precipitate which formed was collected, triturated with 3 Nhydrochloric acid, washed thoroughly with water and dried; yield 3.30 g.

Example 6 A solution of 1,6-hexanediamine (0.58 g.; 0.005 mole) in ml.of dioxane plus 18 ml. of 10% sodium hydroxide was added dropwise to asolution of 4.19 g. (0.01 mole) of MAC in 40 ml. of dioxane with icebath cooling and magnetic stirring. After one hour, an excess of 3 Nhydrochloric acid was added. The supernatant was decanted and freshwater added. The gummy solid solidified; wash thoroughly with water;yield 3.81 g.; test for chloride in negative. The infrared spectrumexhibited A (Nujol mull) 2.98u (m.) amide, 5.44 (m.) anhydride, 5.65u(s.) anhydride, 8.18;; (s.) anhydride.

Example 7 A solution of 0.37 g. (0.005 mole) of redistilled 1,3-propanediamine in 5 ml. of dioxane plus 18 ml. of 10% aqueous sodiumhydroxide was added to a solution of 4.19 g. (0.01 mole) of MAC in 40ml. of dioxane at 2025 with magnetic stirring and external cooling. Onehour after the last addition, an excess of 3 N hydrochloric acid wasadded. The solid was triturated in 3 N hydrochloric acid and washedthoroughly in water; yield 3.04 g.; equivalent weight, found 194; theory210.

Example 8 To a solution of 4.19 g. (0.01 mole) of MAC in ml. of pyridinewas added dropwise, during magnetic stirring, a solution of 0.54 g.(0.005 mole) of para-phenylenediamine. One hour after the last addition,an excess of water was added. The solid was collected, triturated with 3N hydrochloric acid, and washed thoroughly with wa ter; yield 3.92 g.;equivalent weight, found 210; theory 218.

Example 9 To a solution of 4.19 g. (0.01 mole) of MAC 15 m1. of pyridinewas added a solution of 0.54 g. (0.005 mole) of meta-phenylenediamine in10 ml. of pyridine, slowly, with ice bath cooling. A slush formed.Pyridine (35 ml.) was added and after one hour at room temperature, an

8 excess of 3 N hydrochloric acid was added with cooling. Theprecipitate that formed was collected and washed thoroughly with water;yield 4.0 g.; equiv. wt.: found 219; theory 219 for the bisamide.

Example 10 A solution of 0.99 g. (0.005 mole) of 4,4'-methylenedianilinein 10 ml. of dioxane plus 18 ml. of 10% aqueous sodium hydroxide wasadded slowly, (with constant shaking) to a solution of 4.19 g. (0.01mole) of MAC in 40 ml. of dioxane during magnetic stirring and withcooling. After 1 hour at room temperature an excess of 3 N hydrochloricacid was added, the solid collected, washed with water, then with 3 Nhydrochloric acid and then thoroughly with water; yield 4.27 g. equiv.wt. found 244; theory 241 for the bisamide.

Example 11 A solution of 0.99 g. (0.005 mole) of 4,4'-methy1enedianilinein 15 ml. of pyridine was added slowly with cooling and stirring to asolution of 4.19 g. (0.01 mole) of MAC in 15 ml. of pyridine. After onehour at room temperature an excess of water was added, the solid collected, triturated with 3 N hydrochloric acid, then washed thoroughlywith water; yield 4.43 g. equivalent weight: found 247; theory 241 forbisamide.

Example 12 To a solution of 0.41 g. (0.00354 mole) of 1,6-hexanediaminein 35 m1. of dry dimethyl formamide was slowly added 3.11 g. (0.00354mole) of the bisamide of MAC and 1,6-hexanediamine with stirring. Thesolution was boiled until two-thirds of the solvent had been removed.The clear solution was placed in an aluminum cup in an oven and heatedto C., then to C. at which point the solvent began to boil off. At thispoint, a spatula could be dipped into the melt and fibers cold-drawnfrom the melt.

Example 13 A mixture of 0.881 g. (0.001 mole) of the bisamide of MACwith 1,6-hexanediamine and 0.116 g. (0.001 mole) of 1,6-hexanediaminewas mortared together and charged to a test tube 150 mm. long and 17 mm.in inside diameter. The test tube was equipped with a thermometerextending to the bottom of the tube. A capillary gas delivery tubeextended below the level of the melt, carrying a rapid stream ofnitrogen. The test tube was heated over an open Bunsen burner flame.Fusion at 320 C. was carried out for 3 minutes. The polyamide-polyimideobtained was a hard glassy solid. The polymer exhibited hmax, (Nujolmull) 2.98; (m.) (amide), 5.67 (m.) (imide), 5.88 (s.) (shoulder)(imide), 13.93,u (m.) (imide). The molecular weight as determined bytitration with base in acetone was about 2140; softening point C.;insoluble in 40% aqueous potassium hydroxide, methyl alcohol, benzene,and pentane. A film was cast on glass from chloroform. A light colored,tough film was obtained.

Example 14 A mixture of 0.839 g. (0.001 mole) of the bisamide of MACwith 1,3-propanediamine and with 0.116 g.

(0.001 mole) of 1,6-hexanediamine was mortared together and fused at 320C. for 3 minutes, as described in Example 13. The molecular weight bytitration with base in acetone, was about 2440; softening point 190 C.;insoluble in pentane, acetonitrile, methyl alcohol, 40% aqueous sodiumhydroxide and concentrated hydrocholoric acid. A film cast on glass fromchloroform was tough and clear with excellent adhesion to glass.

Example 15 A mixture of 0.825 g. (0.001 mole) of the bisamide of1,2-ethanediamine With MAC and 0.116 g. (0.001 mole) of1,6-hexanediamine was mortared together and fused at 320 C. for 3minutes, as described in Example 13. Softening point of thepolyimide-polyamide was 180 C.; insoluble in benzene, 40% potassiumhydroxide, pentane, methanol, ethyl acetate; molecular weight viatitration with base in acetone was 2480. A film was cast on glass fromchloroform and was hard, tough and clear.

Example 16 A mixture of the bisamide of MAC and ethanediamine (0.83 g.;0.001 mole) and 0.11 g. of para-phenylenediamine was mortared togetherand fused at 270 C. for 4 minutes as'described in Example 13. Thepolyimidepolyamide was a hard, glassy solid on cooling; molecular weightby titration with base in acetone was about 4600; softening point 290C.; insoluble in benzene, 3 N hydrochloric acid 40% potassium hydroxide,pentane, methanol, and acetonitrile.

Example 17 The bisamide of MAC and para-phenylenediamine (0.873 g.;0.001 mole) and 0.108 g. of meta-phenylenediamine (0.001 mole) Weremortared together and fused at 320 C. for 4 minutes as described inExample 13. The polyimide-polyamide was a hard glassy solid; molecularweight by titration in acetone with base was about 2160; softening point230 C., insoluble in glacial acetic acid, 40% potassium hydroxide,concentrated hydrochloric acid, benzene, methanol, pentane, ethylacetate and water.

Example 18 A mixture of 0.116 g. (0.001 mole) of 1,6-hexanediaminetogether with the bisamide of MAC (0.873 g.; 0.001 mole) andmeta-phenylenediamine was fused at 320 C. for 3 minutes as described inExample 13. The polyimidepolyamide was obtained as a hard glassy resin;molecular weight by titration with base in acetone 2840; softening point170; insoluble in methanol, benzene, pentane, 40% aqueous sodiumhydroxide, conc. hydrochloric acid and water.

Example 19 A mixture of 0.198 g. (0.001 mole) of 4,4'-methylenedianilineand of 0.963 g. (0.001 mole) of the bisamide of MAC with4,4-methylenedianiline is mortared together and fused at 320 C. for 3minutes as described in Example 13. The polyamide-polyimide is a hardglassy solid and exhibits a molecular weight of about 4200 by titrationwith base in acetone; softening point of 225 C.; insoluble in benzene,glacial acetic acid, methanol, concentrated hydrochloric acid, pentane,acetonitrile, and 40% aqueous potassium hydroxide.

Example 20 A mixture of 0.11 6 g. (0.001 mole) of 1,6-hexanediamine ismixed with 0.873 g. (0.001 mole) of the bisamide of MAC andpara-phenylenediamine and fused at 320 C. for 3 minutes as described inExample 13. A hard glassy polyamide-polyimide was obtained; softeningpoint 255 C.; insoluble in pentane, methanol, benzene, and 40% aqueouspotassium hydroxide; molecular weight by titration in acetone with basewas about 2600.

10 Example 21 A mixture of 0.964 g. (0.001 mole) of the bisamide of MACand 4,4'-oxydianiline plus 0.116 g. (0.001 mole) of 1,6-hexanediaminewas fused as described in Example 13 at 320 C. for 4 minutes. Themolecular weight (titration with base in acetone) was 8440; insoluble inisooctane, methanol, and benzene; softening point 194 C.

Example 23 A mixture of 0.964 g. (0.001 mole) of the bisamide4,4'-oxydianiline and MAC and 0.200 g. (0.001 mole) of 4,4'-oxydianilinewas fused in a test tube as described in Example 13 at 330 C. for 3minutes. The molecular weight (titration with base in acetone) was 4980;softening point 209 C.; insoluble in isooctane, methanol and benzene.

Example 24 To a solution of 11.6 g. of 1,6-hexanediamine (0.10 mole) in40 ml. of dioxane and 18 ml. of 10% aqueous sodium hydroxide was addeddropwise with stirring and at 0-10" C. a solution of 4.19 g. (0.01 mole)of MAC in 40 ml. of dioxane. To the mixture, after 1 hour at roomtemperature, was added an excess of 3 N hydrochloric acid with cooling.The precipitate was collected, weight 1.67 g., equiv. wt. found 182,theory 178, test for chloride ion positive; [a] -7.8 (C.=0.32 inchloroform). The structure of the above compound is:

A portion of the amide-amine-hydrochloride prepared in Example 24 wasplaced in a test tube (150 mm. long and 17 mm. in inside diameter)equipped with a thermometer extending to the bottom of the tube, and acapillary gas delivery tube which extended below the level of the meltand through which passed a rapid stream of nitrogen. The test tube washeated with a Bunsen burner flame. The compound was fused at 290 C. for2 minutes, 320-330 C. for 3 minutes and finally at 335-345 C. for 3minutes under a heavy stream of nitrogen. The resultingpolyimide-polyamide had a head-to-tail structure. It was a hard glass oncooling; molecular weight via titration with base in acetone 2320; thepolymer was insoluble in methanol, isooctane, and ethyl acetate. It hada softening point of 148 C. A portion was dissolved in chloroform and afilm cast on a cold rolled steel plate. A good film was obtained. Itexhibited good adhesion to steel. It had a Sward hardness of 54. Itshowed good resistance to cold water, no

and 2.00 g. (0.01 mole) of 4,4'-oxydianiline was placed in a test tubeequipped as in Example 13 and fused at 285 1 1 C. for 8 minutes under anitrogen stream and then brought to 310 C. for 1 minute. A glassypolyimide-polyamide was obtained on cooling; molecular weight viatitration with base in acetone, 5500. The polymer was insoluble inacetonitrile, benzene, ethyl acetate, pentane, methanol, dioxane, andglacial acetic acid.

A portion of the same mixture of MAC and diamine was fused as describedabove except that a fluidized sand bath was used as a source of heat.Fusion was carried out under a nitrogen stream at 350 C. for 2 hours. Bydipping a glass rod into the hot melt, fibers could be' repeatedly colddrawn by touching the melt to the edge of the tube and pulling.

Example 27 A portion of a mixture of 4.19 g. (0.01 mole) of MAC and 1.16g. (0.01 mole) of 1,6-hexanediamine was heated in a test tube (150 mm.long and 17 mm. in inside diam.- eter) containing a thermometer, at 320C. for about 4 minutes over a Bunsen burner flame as described inExample 13. A constant stream of nitrogen was introduced below thesurface of the melt through a capillary. On cooling, a hard, toughglassy polyimide-polyamide was obtained which had a molecular weight ofabout 5800 based on a titration with base in acetone. The polymerexhibited a softening point of 205210 C. It was insoluble in methanol,benzene, acetone, pentane, ethyl acetate, 40% aqueous potassiumhydroxide and concentrated hydrochloric acid. The infrared absorptioncurve exhibited A (Nujol mull) 298a (m.) amide; 5.66;t (m.) imide;5.85;]. (s.) (shoulder) imide, 13.92/J. (m.) imide. No band at 5.4 (noanhydride). A film was cast on glass of the polymer from chloroformsolution. The film was glassy, hard and tough, exhibited good adhesionto glass, and was very resistant to water.

Example 28 A mixture of 4.19 g. (0.01 mole) of MAC and 0.877 g. (0.0067mole) of 3,3'-iminobispropylamine was mortared together. The mixture washeated as described in Exam ple 13 to 290 C. for 3 minutes. On cooling ahard, glassy polyamide-polyirnide was obtained, insoluble in benzene,pentane, and 40% aqueous potassium hydroxide. The polymer exhibited asoftening point of 190 C. A film was cast from chloroform solution onglass. A tough glassy film was obtained with good adhesion to glass.

Example 29 A mixture of MAC (0.01 mole; 4.10 g.) and 1,2-ethanediamine(0.01 mole; 0.67 ml.) was fused as described in Example 13, by heatingat 320 C. for about 5 minutes under nitrogen. The molecular weight asdetermined by titration with base in acetone was about 4000. The hard,glassy polyamide-polyimide had a softening point of 290 C. It wasinsoluble in acetonitrile, methyl alcohol, carbon tetrachloride, ethylacetate, benzene, isooctane, 3 N aqueous hydrochloric acid and aqueoussodium hydroxide.

Example 30 A mixture of 4.19 g. (0.01 mole) of MAC and 0.82 ml. (0.01mole) of 1,3-propanediamine was fused as described in Example 13 at 320C. for 2 minutes. The resulting polyamide-polyimide has a softeningpoint of 240 C., and was insoluble in pentane, benzene, acetonitrile andmethyl alcohol.

Example 31 A mixture of 4.19 g. (0.01 mole) of MAC and 1.08 g. (0.01mole) of para-phenylene-diamine Was fused as described in Example 13 at320 C. for about eight minutes. The molecular weight of the resultingpolyimidepolyamide via titration with base in acetone was 7520, and itssoftening point was 335 C. The polyamide-polyimide was insoluble inconcentrated hydrochloric acid, 50% aqueous sodium hydroxide, ethylacetate, benzene, water, ethyl a cohol, acetonitrile, carbontetrachloride, and di- 12. oxane. This polymer could be cold drawn intofibers from a hot melt.

Example 32 A mixture of 4.19 g. (0.01 mole) of MAC and 1.08 g. (0.01mole) of meta-phenylenediamine is heated as described in Example 13 at315 C. for about five minutes. The hard glassy polyimide-polyamide thatwas formed exhibited a softening point of 262 C. It was insoluble in 3 Nhydrochloric acid, water 40% aqueous potassium hydroxide, ethyl alcohol,benzene, pentane, glacial acetic acid, and acetonitrile; The polymer hada molecular Weight of aout 6620 via titration with base in acetone.

Example 33 A mixture of 4.19 g. (0.01 mole) of MAC and 1.98 g. (0.01mole) of 4,4'-methylenedianiline was fused together as described inExample 13 at 320 C. for about five minutes. A hard glassypolyamide-polyimide was obtained on cooling. The polymer exhibited asoftening point of 360 C. It is insoluble in benzene, carbontetrachloride, ethyl acetate, pentane, ethyl alcohol, water,acetonitrile, glacial acetic acid, dioxane, 10% sodium hydroxide and 3 Nhydrochloric acid. The polymer exhibited a molecular weight asdetermined by titration with base in acetone of 11,000; n =009 (c.=l.0,30 C. DMF); nitrogen analysis 5.09% (theory for polyimide-amide 4.98%).A sample of the polymer was fractionated by adding benzene to achloroform solution. The first fraction (13%) exhibited n 0.114 (c.=1.0,30 C., DMF). The second fraction [31%; n 0.089 (c.=1.0, 30 C., DMF)]exhibited a molecular weight of 6072 via vapor pressure osrnometry;nitrogen analysis 4.99% (theory for polyimide-amide 4.98%). The infraredspectrum (Nujol mull) exhibited bands at 3 (s.) (amide), 5.65 (m.)(imide), 5.88 (s.) (imide), 6.11 (s.) (amide), 6.62 (m.) (amide), 13.92(m.) (imideht.

Example 34 A solution of 8 g. of MAC in ml. of absolute methanol wasrefluxed three hours, stripped under reduced pressure to dryness, theresidue taken up in ether, the ether washed with water until neutral,the solvent then removed under reduced pressure and the triester dried.

A mixture of 4.47 g. (0.01 mole) of the trimethyl ester prepared inExample 34 and 1.16 g. (0.01 mole) of 1,6- hexanediamine was mortaredtogether and a portion placed in a test tube equipped as in Example 13.The test tube was placed in a fluidized sand bath and fused at 280 C.for 1 hour under a vigorous stream of nitrogen. The polymer was obtainedas a light yellow glassy solid on cooling. It exhibited the followinginfrared maxima: (Nujol mull) k 3 t, 5.67, 5.83, 5.90, 5.95, 11.90,indicating the presence of amide and imide bands but no anhydride (nobands in 5.45 region); When the polymer was dissolved in chloroform andcast on a glass plate it gave a good film, very pale yellow in color, ofSward Hardness of 46. The film was completely resistant to water forover four hours. On standing overnight in contact with water a whitecoloration appeared which disappeared after standing one-half hour inthe absence of water.

13 Example 36 A mixture of 2.24 g. (0.005 mole) of the triester of MACprepared as in Example 34 and 1.00 g. (.005 mole) of 4,4-oxydianilinewas prepared and a portion of it was placed in a test tube equipped asin Example 13 and placed in a fluidized sand bath where it was fused at285 C. for 1.5 hours and then at 310 C. for 1 hour. The hot product atthis point could be cold drawn into fibers by inserting a glass rod intothe melt, touching the lip of the test tube with the polymer andpulling.

The polymer on cooling exhibited a softening point of 205 C. and wasinsoluble in isooctane, ethyl acetate. benzene and methanol.

Example 37 A solution of 8.11 g. (0.02 mole) of MAC in 36 ml. of dryl-methyl-Z-pyrrolidone was added slowly at -15" C. to a solution of 2.32g. (0.02 mole) of 1,6-hexanediamine in 27 m1. of 1-methyl-2-pyrrolidonein which was dispersed 2.12 g. (0.02 mole) of finely divided anhydroussodium carbonate. Vigorous stirring was supplied. The solution wasallowed to stand at room temperature for 30 minutes and filtered; n 0.07at 30 C. A portion was diluted with water. The white precipitate wascollected and found to be insoluble in DMF, acetone, and concentratedalkali and acid, molecular weight via vapor pressure osmometry 3753;nitrogen analysis 5.83%, calculated for poly (half amide) 5.62%. Aportion of the 1-methyl-2-pyrrolidone solution was heated to 190 C. andcooled. The polymer was precipitated with water, 7 3.0 (w.) (amide),5.64 (m.) (imide), 5.88 (s.) (shoulder) (imide), 6.07 (s.) (amide),6.56 1. (m.) (amide). I r

We claim:

1. A polyirnide-polyamide resin, the repeating units of which exhibit arandom orientation, wherein the repeating unit is selected from thegroup consisting of and and wherein 14 2. A polyimide-polyamide resin,the repeating units of which exhibit an ordered orientation, wherein therepeating unit consists essentially of the structure:

0 x x 2 x 2WD and v 3. A process for preparing a polyimide-polyamide,the repeating units of which exhibit a random orientation,

wherein the repeating unit is selected from the group consisting of L-Q- -Q l and wherein X is which process consists in its entirety offusing at a temperature of about from 225 to 375 C. and for an inter- 1516 val of time of about from three to eight minutes a 1:1 and mole ratioof the compound represented by the structure:

0 II which process consists in its entirety of fusing at a CH8 0 5temperature of about from 290 to 370 C. and for an H C interval of timeof about from three to eight minutes a 3 compound represented by thestructure: CH: O

ll O 10 CHa H03 I Cg: O C a 0:0 CH1;

l ii and a diamme selected from the group consrstmg of HzN-CHg CH2 'NHg,CH2 0 H8 C NH R NHTH C1 H2N--CH2 CH2 CH2 CH2 CH2 CH2'NH2 wherein R isselected from the group consisting of nm-Q-mn His-Q -CH -CH2,CH2'CH2'CHz- N112 CH CH CH CH CH CH 5. A polyimide-polyamide resin, therepeating units of 4. A process for preparing a polyimide-polyamide, thewhich exhibit an ordered orientation, wherein the repeatrepeating unitsof which exhibit an ordered orientation, ing unit consists essentiallyof the structure:

and

I M t CH, H30 in N H5O 43H: JHz if "i 0 b c 1 (fiN-R-l l(f CH:

0 H H 5 wherein the repeating unit consists essentially of the and R isselected from the group consisting of structure: 0 --CHg'CHz-,'-CH2CH2'CH2,

g --CH -CH -CH -CH -CH -CH and and R is selected from the groupconsisting of --(}H .CH .OH CH .CH .CH .QH .CH CH; 6. process forpreparing a polyimide-polyamide, the repeating units of which exhibit anordered orientation,

-. r wherein the repeating unit consists essentially of the structure:

and R is selected from the group consisting of:

CHz-CH2, -CH2-CH2-CH2, -CHz-CH2-CH2'CHz'CHz-CH2 which process consistsin its entirety of fusing at a temperature of about from 225 to 375 C.and for an interval of time of about from two to eight minutes a 1:1mole ratio of the compound represented by the structure:

E0 CH; H30 0 C 18 and a diamine represented by the structure H N-R-NH inwhich structures R is selected from the group consisting of:

5 -CH2-CHz-, CHz-CH2-OH2, CHz-CHrCHrCHz-CHz-CHZ] 10 and 0 ll CH 0 CHIReferences Cited UNITED STATES PATENTS 3,355,427 11/1967 Loncrini 260-473,373,171 3/1968 Lucas et a1. 260-3468 WILLIAM H. SHORT, PrimaryExaminer L. L. LEE, Assistant Examiner U.S. C1. X.R.

